US3169994A - Preparation of tertiary alkyl amines - Google Patents

Preparation of tertiary alkyl amines Download PDF

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Publication number
US3169994A
US3169994A US125671A US12567161A US3169994A US 3169994 A US3169994 A US 3169994A US 125671 A US125671 A US 125671A US 12567161 A US12567161 A US 12567161A US 3169994 A US3169994 A US 3169994A
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bromide
ammonia
alkyl
reaction
mixture
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US125671A
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English (en)
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Roy Gustave
Colson Louis
Decuypere Maurice
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/08—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings

Definitions

  • This invention relates to a process for the preparation oftertiary amines.
  • alkyl bromides on monoalkylamines or dialkylamines, by heating the mixture of alkyl bromides and amines to about 120-160 C. in the presence of gaseous ammonia, which acts preferentially as a hydrogen bromide acceptor without notably reacting with the alkyl bromides (with the formation of amines), in a way not previously obtainable.
  • the catalyst for instance cuprous iodide, is used in the usual catalytic proportions, preferably about 1% by weight of the reaction mixture.
  • the alkyl radicals of the reactants having at least six carbon atoms and being those of the trialkylamine to be prepared, the reaction mixture being heated to a temperature from 120 C. to 175 C.
  • the ammonia acts as an acceptor for the hydrogen bromide formed by the action of the alkyl bromide on the amine or amines.
  • the reaction is carried out in the presence of a catalyst derived from copper.
  • a catalyst is not essential, but it enables operation to be effected at a temperature approximately 15 C. below theternperature of the reaction in the absence of a catalyst, which is particularly advantageous since the instability ofthe desired amines increases very rapidly with temperature.
  • the invention more particularly concerns a method of operation, applied to the preparation of amines having three identical hydrocarbon radicals each having eight -to eighteen carbon atoms, such amines being utilisable as ion exchangers, for example in the purification of solutions of uranium or other actinides.
  • long-chain trialkylamines namely, those in which the alkyl groups include a large number of carbon atoms, for example, more than six, can be obtained, by treating monoalkylamines or dialkylamines with alkyl bromides in the presence of alkali metal hydroxides or carbonates (for example, potassium hydroxide or sodium carbonate), which act as hydrogen bromide acceptors, but the yields of the tertiary amine are very low, because of the considerable formation of an ethylenic hydrocarbon by dehydrobromination of alkyl bromide (dehydrobromination consists in the evolution of hydrogen bromide,
  • alkali metal hydroxides or carbonates for example, potassium hydroxide or sodium carbonate
  • cuprous iodide act as catalysts which favour the replacement of a halogen atom by an amine radical.
  • cuprous iodide cannot be used in the presence of-a hydrogen halide acceptor of alkaline character, because the iodide is decomposed by alkalies.
  • the inventors have made the surprising discovery that trialkylamines can be obtained in excellent yields, particularly trialkylamines in which the alkyl radicals have more
  • the gaseous ammonia also has the advantage of not materially decomposing the cuprous iodide.
  • cuprous'iodide is particularly advantageous, since it appears that the catalytic action of the copper ion is added to that of the iodine ion, which tends to replace the bromine to form an alkyl iodide which is more reactive than the alkyl bromide.
  • the steric hindrance of iodine which is less than that of bromine, enhances the reactivity.
  • two alkyl radicals of a secondary amine employed can be the same or difierent.
  • the reaction preferably takes place at atmospheric pressure, at a temperature between about C. and C., in the presence of about 0.1 mole of cuprous iodide per mole of amine used as a reactant.
  • this salt can take the form of very fine microcrystals, wihch make the reaction medium very viscous and diificult to agitate towards the end of the reaction. Also, the ammonium bromide precipitate can be very diificult to separate by filtration. These difiiculties can be avoided by adding a little water to the reaction medium at the end of the reaction, which has the effect of enlarging the ammonium bromide crystals, which-thus become readily filterable.
  • the yields of the trialkylamine relative to the monoalkylamine or relative to the dialkylamine reach 95% of the theoretical and the formation of ethylenic hydrocarbons is minimal.
  • Example I Preparation of trilaurylamine by reaction of lauryl bromide on monolaurylamine in the presence of ammonia and cuprous iodide 92.5 g. (0.5 mole) of monolaurylamine, 274 g. (1.1 moles) of lauryl bromide, i.e. a excess with respect to the stoichiometric proportion, and 1 g. (about 0.1 mole per mole of base) of cuprous iodide were introduced into a l-litre, 3-neck, ground-joint flask provided with very eificient agitation, an ammonia inlet tube terminating at the bottom of the flask, a thermometer and an upright reflux condenser.
  • cuprous iodide 92.5 g. (0.5 mole) of monolaurylamine, 274 g. (1.1 moles) of lauryl bromide, i.e. a excess with respect to the stoichiometric proportion, and 1 g
  • the agitator was started and the reaction mixture was heated to l50160 C., whereupon ammonia was introduced (about 200 bubbles/minute). Precipitation of microcrystalline ammonium bromide occurred, which made the medium very viscous and difficult to agitate efiiciently. 1 ml. of distilled water was added to enlarge the crystals of ammonium bromide; the reaction medium became more fluid and easier to agitate. After heating for 2 /2 hours with ammonia input, the amount of gas leaving the flask was the same as the input (the amounts being measured under the same conditions of temperature and pressure).
  • reaction mixture was allowed to cool, filtered on paper and the filtrate (organic layer) was washed with water, then with a normal potash solution and finally again with water. If decantation is found to be too difiicult, because of the formation of emulsions, the water can be replaced by methanol to facilitate this operation.
  • the precipitate recovered on the filter consisting mainly of ammonium bromide, was dissolved in water and the aqueous phase so obtained was extracted with ether. The ethereal layer was separated and, after eliminating the ether by evaporation, the residue was united with the organic phase previously obtained by washing the filtrate.
  • the trilaurylamine was thus obtained at an overall conversion of 91% with respect to the monolaurylamine and in a yield of 97.5%, taking into account the lauryl bromide, monolaurylamine and dilaurylamine recovered. Dehydrobromination of the lauryl bromide was thus negligible.
  • the mixture was filtered cold and the filtrate was washed with water, then with a methanolic potash solution (5.6 g. potassium hydroxide in 60 ml. of methanol) and again with water until neutral to phenolphthalein.
  • a methanolic potash solution 5.6 g. potassium hydroxide in 60 ml. of methanol
  • the precipitate recovered on the filter which was mainly ammonium bromide, was dissolved in water and the aqueous phase obtained was extracted with ether.
  • the ethereal layer was separated and, after eliminating the ether by evaporation, about 5 g. of a residue was obtained, constituted by a yellowish viscous oil which was united with the organic phase previously obtained by washing the filtrate.
  • the trilaurylamine was thus obtained at an overall conversion of 90% with respect to the dilaurylamine and in a yield of 96.5%, taking into account the lauryl bromide and dilaurylamine recovered.
  • a process as described in claim 1 including the step of adding to said mixture about 1% by Weight of said mixture of cuprous iodide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US125671A 1960-08-10 1961-07-21 Preparation of tertiary alkyl amines Expired - Lifetime US3169994A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR835547A FR1272136A (fr) 1960-08-10 1960-08-10 Perfectionnements apportés à la préparation des amines tertiaires

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US3169994A true US3169994A (en) 1965-02-16

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US (1) US3169994A (enrdf_load_stackoverflow)
BE (1) BE606516A (enrdf_load_stackoverflow)
CH (1) CH404684A (enrdf_load_stackoverflow)
FR (1) FR1272136A (enrdf_load_stackoverflow)
GB (1) GB974623A (enrdf_load_stackoverflow)
LU (1) LU40424A1 (enrdf_load_stackoverflow)
SE (1) SE302134B (enrdf_load_stackoverflow)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4595773A (en) * 1985-01-24 1986-06-17 General Electric Company Method for preparing copper-diamine complexes and diamines

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1932518A (en) * 1928-08-31 1933-10-31 Dow Chemical Co Method of making primary amino compounds
US2192523A (en) * 1937-03-08 1940-03-05 Sharples Solvents Corp Ammonolysis of secondary and tertiary amines

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1932518A (en) * 1928-08-31 1933-10-31 Dow Chemical Co Method of making primary amino compounds
US2192523A (en) * 1937-03-08 1940-03-05 Sharples Solvents Corp Ammonolysis of secondary and tertiary amines

Also Published As

Publication number Publication date
CH404684A (fr) 1965-12-31
LU40424A1 (enrdf_load_stackoverflow) 1961-09-21
FR1272136A (fr) 1961-09-22
BE606516A (fr) 1961-11-16
GB974623A (en) 1964-11-11
SE302134B (enrdf_load_stackoverflow) 1968-07-08

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